Electrically conductive cofacially crystallizing organomacrocycle forming compositions

ABSTRACT

Methods and formable compositions for fabricating electrically conductive articles comprising cofacially stacking organomacrocycles and as cofacially stacking phthalocyanines, in which a composition comprising a cofacially stacking phthalocyanine in strong Bronsted acid is formed into a desired shape such as a fiber or film, solidified by removal of the solvent, and provided in fractional valence state.

RELATED APPLICATION AND GOVERNMENT RIGHTS STATEMENT

This application is related to contemporaneously filed applicationentitled "Electrically Conductive Low Dimensional OrganomacryocycleCompositions, Articles and Fabrication Methods". The U.S. Government hasrights in this invention Pursuant to grants N00014-81-K-0445 from theOffice of Naval Research and DMR79-23573 from the National ScienceFoundation.

This is a division of application Ser. No. 451,408, filed 12/20/82 nowU.S. Pat. No. 4,563,300.

FIELD OF THE INVENTION

The present invention is directed to low dimensional electricallyconductive organomacrocycle compositions and articles, to methods formanufacturing such electrically conductive articles, such as extruded,cast and to printed fibers and films, and compositions for fabricatingsuch electrically conductive articles.

BACKGROUND OF THE INVENTION

Various types of organic, metalloorganic and inorganic materials such aspolymeric sulfur nitride, polyacetylenes, polyphenylenes, polypyrroles,polythiophenes, polyphenylene sulfides and ion-radical salts are knownwhich have unusual, highly anisotropic and potentially usefulelectrical, optical and/or magnetic properties [J. T. Devreese, et al.,eds., "Highly Conducting One-Dimensional Solids", Plenum Press, New York(1979); W. E. Hatfield, ed., "Molecular Metals", Plenum Press, New York(1979); J. B. Torrance, "The Difference Between Metallic and InsulatingSalts of Tetracyanoquiniodimethane (TCNQ): How to Design an OrganicMetal", Accts. Chem. Res., 12, 79 (1979); J. S. Miller, et al., eds.,"Synthesis and Properties of Low-Dimensional Materials", Ann. NY Acad.Sci., 313 (1979); H. J. Keller, ed., "Chemistry and Physics ofOne-Dimensional Metals", Plenum Press, New York (1977)]. Such materialshave stimulated significant research activity in respect to the basicchemistry and physics of such materials. Furthermore, substantialefforts have been directed toward applications utilizing such materials,such as sensors [S. Yoshimura, et al., "Solid State Reactions in OrganicConductors and Their Technological Applications", Ann. NY Acad. Sci.,269 (1979); S. D. Senturia, et al., "Charge-Flow Transitor: A New MOSDevice", Appl. Phys. Lett., 30, 106 (1977)], rectifiers [A. Aviram, etal., "Molecular Rectifiers", Chem. Phys. Lett., 29, 27 (1974)],switching devices [R. S. Potember, et al., "A Reversible Field InducedPhase Transition in Semiconducting Films of Silver and Copper TNAPRadical-Ion Salts", J. Am. Chem. Soc., 102, 3659 (1980)], photoresists[Y. Tomkiewicz, et al., "Organic Conductors as Electron Beam ResistMaterials", Extended Abstracts, Electrochemical Society Spring Meeting,St. Louis, May, 1980, No. 63.], fuel cells, chemoselective electrodes[S. Yoshimura, "Potential Applications of Molecular Metals", PlenumPress, p. 471, New York (1979); C. D. Jaeger, et al., "ElectrochemicalBehavior of Donor-Tetracyanoquinodimethane Electrodes in Aqueous Media",J. Am. Chem. Soc., 102, 5435 (1980)], solar energy conversion elements[C. K. Chiang, et al., "Polyacetylene, (CH)_(x) : n-type and p-typeDoping and Compensation", Appl. Phys. Lett., 33, 78 (1978); M. Ozaki, etal., "Semiconductor Properties of Polyacetylene p-(CH)_(x) :n-CdSHeterojunctions", J. Appl. Phys., 51, 4252 (1980)] andelectrophotographic devices, as well as durable synthetic materials toreplace metals [E. M. Engler, et al., "Potential Technology Directionsof Molecular Metals", Plenum Press, p. 541, New York (1979)]. However,despite the scientific advances which have been achieved, understandingand ability to exert chemical or manufacturing control in the practicalutilization and application of such materials is at a relativelyprimitive level, thus representing a barrier to practical utilization oforganoconductive materials. Major difficulties in the utilization ofsuch organoconductive materials may include undesirable physical ormechanical properties of the material itself, instability of thematerial with respect to air or moisture, adverse effects of processingsteps on conductivity, thermal intractability or instability, and/orinsolubility in common solvents. In this latter regard, processingtechniques such as fiber spinning and film casting or extrusion whichare important for practical applications, are only possible if thematerial can be melted or brought into the solution phase.

Molecular arrays of planar, highly electron delocalized, polarizablemolecules which form mixed valence, stacked crystalline lattices, suchas metallophthalocyanine halides (e.g., nickel phthalocyanine iodides)exhibit significant low dimensional (e.g., substantially one-dimensionalalong the stacking direction) electrical conductivity and have desirablethermal stability, but are not readily obtained in desired forms orstructures for practical use. In such stacked, electrically conductivemolecular arrays, the subunit component moieties are positioned in closespatial proximity, and in crystallographically similar environments,with sufficient intermolecular orbital overlap to provide a continuouselectronic pathway for carrier delocalization. Substantial researcheffort has been applied to the theoretical understanding of theproperties and conductive mechanism of such materials [T. J. Marks, etal., Chapter 6, "Highly Conductive Halogenated Low-Dimensional Materialsin Extended Linear Chain Compounds", Vol. 1, Plenum Press (1982), J. S.Miller, ed.]. The properties of such materials are typically measuredfrom compressed pellets or carefully grown crystals.

Low-dimensional mixed-valent arrays of planar, conjugatedmetallomacrocyclic donor moieties such as glyoximates [M. A. Cowie, etal., "Rational Synthesis of Unidimensional Mixed Valence Solids.Structural, Spectral and Electrical Studies of Charge Distribution andTransport in Partially Oxidized Nickel and PalladiumBisdiphenylglyoximates", J. Am. Chem. Soc., 101, 2921 (1979); T. J.Marks, et al., "Assessing the Degree of Partial Oxidation inOne-Dimensional Conducting Iodides", J. Chem. Soc., Chem. Commun., 444(1976); L. D. Brown, et al., "Rational Synthesis of Unidimensional MixedValence Solids, Structure-Oxidation State-Charge Transport Relationshipsin Iodinated Nickel and Palladium Bisbenzoquinodioximates", J. Am. Chem.Soc., 101, 2937 (1979)], phthalocyanines [J. L. Petersen, et al., "A NewClass of Highly Conductive Molecular Solids: The Partially OxidizedPhthalocyanines", J. Am. Chem. Soc., 99, 286 (1977); C. S. Schramm, etal., "Chemical, Spectral, Structural and Charge Transport Properties ofthe `Molecular Metals` Produced by Iodination of NickelPhthalocyanines", J. Am. Chem. Soc., 102, 6780 (1980)], andtetraazanulenes [L. S. Lin, et al., "New Class of ElectricallyConductive Metallomacrocycles: Iodine-dopedDihydrodibenzo[b,i][1,4,8,11]tetraazacyclotetradecine Complexes", J.Chem. Soc. Chem. Commun., 954 (1980)] having an MN₄ planar ligand corestructure have been extensively studied by reason of their electricallyconductive proporties. These cofacially stacking materials arecocrystallized with appropriate acceptor moieties such as bromine oriodine oxidants. When successful, such cocrystallization may provide acrystal structure composed of segregated (i.e., donors and acceptors inseparate columns), partially oxidized metallomacrocyclic stacks andparallel arrays of halide or polyhalide counterions. The cofaciallystacking subunits of the metallomacrocyclic stacks generally havefractional valence as a consequence of incomplete charge transfer fromthe cofacially stacking donor subunits to the associated acceptormoieties. For example, nickel phthalocyanine iodide [Ni(Pc)]I₁.0 may becrystallized in stacks of rotationally staggered cofacially arrayedNi(Pc)⁺⁰.33 columns surrounded by parallel chains of I₃ ⁻ counterions inwhich conductivity is predominantly a ligand-centered phenomenon alongthe stacking direction of the nickel phthalocyanine columns.

Unfortunately, the lattice architecture of ionicly bonding materialsdepends upon the largely unpredictable and uncontrollable forces thatdictate the stacking patterns, the donor-acceptor orientations, and thestacking repeat distances, such that a common pitfall in the design ofnew materials is that segregated stacks do not form. This problemseverely limits the ability to design and tailor microstructures whichlead reliably to electroactive molecular assemblies. Moreover there aresubstantial difficulties in providing such material in useful form.Furthermore, while such materials may be provided in powder or largercrystalline form, or in evaporated film form, these materials tend to befrangible and to have limited mechanical strength.

Control of cofacial stacking may be carried out by covalently bondingmacromolecular subunits in cofacial stacking array, and substantial workhas been carried out in the provision of covalently bonded, cofaciallystacking polymers such as Group IV metallophthalocyanine, porphyrin andtetraazaannuelene polymers [R. D. Joyner, et al., "GermaniumPthalocyanines", J. Am. Chem. Soc., 82, 5790 (1960); M. K. Lowery, etal., "Dichloro(phthalocyanino)silicon" Inorg. Chem., 4, 128 1965); W. K.Kroenke, et al., "Octahedral Silicon-Oxygen, Germanium-Oxygen, andTin-Oxygen Bond Lengths from Interplanar Spacings in the PhthalocyaninoPolymers (PcSiO)_(x), (PcGeO)_(x), and (PcSnO)_(x) ", Inorg. Chem., 2,1064 (1963); Marks, et al., supra], particularly including polysiloxaneand polygermyloxane stacking stabilized polymers, and fluoro-aluminumphthalocyanine polymers, such as [Al(Pc)F]_(n) and [Ga(Pc)F]_(n), whichare isoelectronic therewith [U.S. Pat. No. 4,304,719].

The covalent bonds which hold such cofacial arrays together aresignificantly stronger than packing, van der Walls, and band formationforces of ionicly bonding cofacially stackable materials which do notutilize such covalent stacking stabilization. However, such materialsare similarly typically formed and studied as powders, particles orcompressed pellets, and the practical utilization of such materials hasbeen restricted for reasons including the lack of practical fabricationmethods for these materials.

There is accordingly a need for methods and compositions for fabricatingcofacially stacking electroconductive materials such as phthalocyaninesinto electroconductive articles having desirable thermal, hydrolyticand/or oxidative stability in addition to desirable mechanical andelectroconductive properties, and for electroconductive compositions,articles and devices utilizing such cofacially stackingelectroconductive materials.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view, partially broken away, llustrating a fiberspinning syringe apparatus of the type utilized for preparation ofelectrically conductive fibers from cofacially stackingorganomacrocyclic compositions described in various Examples of thepresent disclosure;

FIG. 2 is a log conductivity vs. inverse temperature graph of electricalconductivity measurements relating to an iodine-doped, fractionalvalence nickel phthalocyanine: aramid fiber prepared from a concentratedforming composition solution by means of a fiber spinning syringe likethat of FIG. 1;

FIG. 3 is a conductivity vs. inverse temperature graph of electricalconductivity measurements relating to a bromine-doped fractional valencephthalocyanine siloxane polymer: aramid fiber prepared from aconcentrated forming composition solution by means of a fiber spinningsyringe like that of FIG. 2;

FIG. 4 is a conductivity vs. inverse temperature graph of electricalconductivity measurements relating to an iodine-doped fractional valencephthalocyanine siloxane polymer: aramid fiber prepared from aconcentrated forming compositions solution by means of a fiber spinningsyringe like that of FIG. 2;

FIG. 5 is a log conductivity vs. inverse temperature graph of electricalconductivity measurements relating to a bromine-doped fractional valencephthalocyanine siloxane polymer: aramid fiber prepared from aconcentrated forming composition solution by means of a fiber spinningsyringe like that of FIG. 2;

FIG. 6 is a conductivity vs. inverse temperature graph of electricalconductivity measurements relating to an iodine-doped fractional valencephthalocyanine siloxane polymer: aramid fiber prepared from aconcentrated forming composition solution by means of a fiber spinningsyringe like that of FIG. 2 and iodine (I₃ ⁻) containing coagulationbath;

FIG. 7 is a conductivity vs. inverse temperature graph of electricalconductivity measurements relating to an iodine-doped, fractionalvalence nickel pthalocyanine: aramid fiber like that of FIG. 6 buthaving a different proportion of phthalocyanine component;

FIG. 8 is a log conductivity vs. inverse temperature graph of electricalconductivity measurements relating to another embodiment of anelectrically conductive, fractional valence nickel phthalocyanine:aramid fiber which is bromine doped after spinning;

FIG. 9 is a conductivity vs. inverse temperature graph of anotherembodiment of an electrically conductive fractional valence iodinatednickel phthalocyanine: aramid fiber like that of FIG. 2, utilizingiodinated nickel phthalocyanine to provide the forming compositionsolution;

FIG. 10 is a cross sectional view of a compound extrusion apparatusadapted for fabrication of composite electroconductive fibers; and

FIG. 11 is an illustration of an electroconductive printed circuitdevice utilizing a forming composition in accordance with the presentdisclosure.

DESCRIPTION OF THE INVENTION

Generally, the present disclosure is directed to methods for fabricatingelectrically conductive articles comprising a fractional valencecofacially stacking organomacrocyclic component. In accordance with suchmethods, conductive articles of predetermined form such as sheet orfiber form may readily be provided as well as more intricate structures,such as composite structures and electronic circuit structures. Thepresent disclosure is also directed to formable compositions forfabricating electrically conductive articles comprising cofaciallystacking fractional valence organomacrocycle components, and to theformed, electroconductive articles themselves.

The provision and utilization of forming compositions for fabricatinglow dimensionally electroconductive articles is an important feature ofthe present disclosure. Such forming compositions may be readilyutilized in the fabrication methods to be described in detail herein,and may comprise a fiber-forming solution comprising a strong Bronstedacid solvent and at least about 5 weight percent and perferably at leastabout 10 percent by weight, based on the total weight of said solution,of a polymeric cofacially stacking porphyrazine, which is covalentlybonded in cofacially stacking array, dissolved in such solvent. Thebonded porphyrazine polymer such as a phthalocyanine siloxane polymer,should desirably have a subunit stacking distance of less than about3.58 Angstroms. The forming composition solutions will desirably have aviscosity of at least about 200 centipoise in a temperature range offrom about 50° C. to about 90° C. The forming solution composition mayhave substantially greater viscosity, and may be gelled, particularly atlower temperatures, but will exhibit plastic deformation under shearingconditions which permits the composition to be formed into a desiredshape prior to solvent removal.

The forming compositions may further comprise so.lid components such aselectroconductive, magnetic or reinforcing powders or fibers, which arenot dissolved in the strong Bronsted, acid solvent, but which aredesired in a finished conductive article to be manufactured from theforming composition. Forming compositions for fabricating lowdimensionally electroconductive articles may also be provided whichcomprise an alloying polymer in addition to a cofacially stackingorganomacrocycle dissolved in the strong Bronsted acid solvent. In thisregard, such compositions may comprise at least about three percent byweight, based on the total weight of said solution, of a cofaciallystacking porphyrazine, and at least about three weight percent of analloying polymer dissolved in a strong Bronsted acid solvent. Thealloying polymer is desirably a polyamide such as an aramid polymer offiber forming molecular weight, which has a strong tendency tocrystallize, particularly in a predominantly uniaxial or longitudinalmanner.

In accordance with method aspects of the present disclosure, lowdimensionally electroconductive articles may be readily fabricated byproviding a fiber forming composition comprising a solution ofcofacially stacking organomacrocyclic porphyrazine component dissolvedin a strong Bronsted acid solvent, forming the composition into apredetermined shape, solidifying the shaped composition by removing atleast a portion of the solvent and subjecting the cofacially stackingporphyrazine component to redox conditions to provide a fractionalvalence conductive state. The forming of the organomacrocyclecomposition into a predetermined shape may desirably be carried out byextruding the composition through an orifice of predetermined shape, andthe Bronsted solvent may desirably be removed by contacting said shapedcomposition with a suitable coagulating fluid, as will be more fullydescribed.

Extrusion techniques may be utilized to provide electroconductive fibersand films. The extrusion orifice may be a single orifice for providing aformed article of substantially homogeneous composition, or a compoundorifice for coextruding multiple compositions at least one of which isan organomacrocyclic forming composition in accordance with the presentdisclosure, to provide a composite formed electroconductive article.However, other forming techniques, such as coating or spraying theorganomacrocyclic forming composition on a suitable substrate, orprinting a predetermined pattern such as a complex circuit shape on asuitable substrate, may also be employed.

In accordance with various method aspects of the disclosure, a film orfiber forming solution of a cofacially stacking low dimensionalmacrocyclic organoconductor is provided in a strong Bronsted acidsolvent, and the solution is formed into a desired shape in a suitablemanner, such as by extrusion. At least a portion of the solvent issubsequently removed from the formed article, to solidify theorganoconductor component in cofacially stacked array while maintainingthe article form. The low dimensional cofacially stackingorganoconductor component is subjected to redox treatment to provide theorganoconductor in a conductive, fractional valence state.

As also indicated, various aspects of the present disclosure are alsodirected to the formed low dimensional electroconductive articlesthemselves, comprising a matrix of at least about five and preferably atleast about 50 weight percent, based on the total weight of theconductive article, of a solid blend of a coprecipitated cofaciallystacking fractional valence porphyrazine organomacrocycle component, andan alloying polymer. The coprecipated blend itself should desirably havethe porphyrazine and the alloying polymer in weight ratio of at least1:3 cofacially stacking porphyrazine to alloying polymer, and morepreferably at least about 1:1. Conductive fibers and conductive sheetsare useful forms of such conductive articles, which in conductive formwill generally also comprise a fractional valence counterion componentin intimate admixture with the fractional valence cofacially stackingorganomacrocycle component. The conductive article may further comprisediscrete solid components such as electrically conductive, magneticand/or reinforcing particles or fibers dispersed in the organomacrocyclealloying polymer blend, in amounts up to 75 volume percent of the blend.

In accordance with various preferred aspects of the present disclosure,it has been determined that relatively concentrated solutions ofcofacially stacking porphyrazine organoconductive materials which arecovalently bound in cofacial array such as silicon phthalocyaninepolymers [Si(Pc)O]n, may be provided in strong Bronsted acid solventssuch as trifluoromethanesulfonic acid ["triflic acid" HSO₃ CF₃ ]. It isimportant to provide a significant concentration of the cofaciallystacking porphyrazine dissolved in the strong Bronsted acid solvent sothat a solution composition may be formed and have the solvent removedtherefrom to provide a form-stable conductive article. In this regard,for example, electrically conductive fibers of phthalocyanine siloxanepolymers can be spun from relatively concentrated solutions of[Si(Pc)O]n in strong Bronsted acids, HSO₃ CF₃ being particularlypreferred. Even a simple, prototype wet-spinning apparatus 100consisting of a syringe 102 warmed with heating tape (not shown) andequipped with a 5 mm, 22-25 gauge needle, and a clamp to force thesyringe plunger down and the polymer solution 106 into an aqueousprecipitating bath 108, such as illustrated in FIG. 1 may be utilized toprovide dark purple fiber(s) 110 of [Si(Pc)O]n. Moreover, spectroscopicand conductivity results suggest that the Bronsted acid solvent may actas an electron-accepting dopant to provide the cofacially stackingphthalocyanine siloxane polymer fibers in conductive, fractional valencestate. Thus, the fiber may be provided in "doped" and electricallyconductive fractional valence state as obtained, e.g., ([Si(Pc)O]n(O₃SCF₃)y)n. Of course, halogens or other acceptors may be utilized tofurther increase the degree of oxidation in provision ofelectroconductive articles. Moreover, forming compositions comprising acofacially stacking porphyrazine organomacrocycle and a reinforcing oralloying polymer component, particularly including aromatic polyamidepolymers (referred to herein as "aramid" polymers) may be formed andsolidified to produce mixed, electrically conductive formed compositionssuch as aramid/([Si(Pc)O] (O₃ SCF₃)_(y) ]_(n) fibers having desirableelectrical and physical properties. Accordingly, while electricallyconductive fibers or other articles of a single material may beprovided, it is a particularly advantageous aspect of compositions andmethods in accordance with the present disclosure that by alloyingcofacially stacking organomacrocyclic components with non-conductingpolymers, such as aramid polymers having a strong tendency tocrystallize, electroconductive articles and compositions with widelytailorable properties may be produced. It should be noted that althoughvarious of the aspects of the present disclosure are described withparticular reference to conductive fiber manufacture as an importantapplication of the present disclosure, additional aspects of the presenttechnology may also be applied to fabrication of electroconductivefilms, to provision of electroconductive coatings on various substrates,and to fabrication of conductive devices or other articles such asrectifiers, photovoltaic devices, photoconductor devices, solar energyconverting devices, temperature and pressure sensors, display devicesand switching devices.

Having generally described various aspects of the present disclosure,specific aspects will now be described in further detail.

As indicated, the forming compositions and conductive articles describedherein generally comprise a cofacially stacking organomacrocycliccomponent having a planar, highly electron delocalized polarizable pielectron configuration. Desirably, the polarizable planarorganomacrocycle subunits have a conjugated pi electron system of atleast 22 electrons. By cofacially stacking is meant that the planarorganomacrocyclic subunits are adapted to align, in solid form, instacked arrays, the individual subunits of which are aligned inface-to-face relationship with the subunit plane substantiallyorthogonal to the stacking axis.

Electrical conductivity in stacked arrays of such organomacrocycles ispredominantly a low-dimensional ligand-centered phenomenon functioningby electron or hole transport along the stacking direction and in thisregard, the stacking distance by which the substantially planarorganomacrocyclic subunits are separated is important in the provisionof conductive properties. The organomacrocyclic component should besthave a subunit stacking repeat distance of less than about 3.58Angstroms, and preferably less than about 3.4 Angstroms. Cofaciallystacking porphyrazines such as phthalocyanines are particularlypreferred as the organoconductive component in forming compositions ofthe present disclosure and articles manufactured therefrom. In thisregard, the cofacially stacking porphyrazine component may be covalentlybound in cofacial array in polymeric form as in the case of siliconphthalocyanine polymers or may be cofacially stacking in columnar arrayby virtue of ionic bonding or other crystallization forces, as in thecase of appropriately crystallized nickel phthalocyanine compositions.Phthalocyanines or other porphyrazines may be substituted orunsubstituted in either the ring or straight chain portions.Organomacrocyclic porphyrazines contemplated herein may be described ascompositions comprising four isoindole groups (pyrrole nuclei) linked byfour nitrogen atoms to form a conjugated planar ligand having in neutralstate a 22 pi electron conjugated system (hereinafter referred to as"Pc"), and having the general formula (Pc)M_(n) where M is hydrogen or apolyvalent transition metal and n is an integer generally having a valueof one, but having a value of two when M is hydrogen. Desirably M is aGroup IV element, or a divalent transition metal. Group Ia, Ib, IIa, IIband VIII elements are particularly contemplated as the component M.Particularly preferred are M components selected from the groupconsisting of hydrogen, nickel and silicon. Porphyrazines may beprepared from ortho-substituted aromatic compounds such as substitutedor unsubstituted 1,2 dinitrilo benzenes or 1,2 dinitrilo naphthalenes,and accordingly will generally comprise additional conjugated bondsystems extending beyond the core porphyrazine, or tetrazaporphineligand. The core porphyrazine ligand is generally substituted, and inthis regard particularly preferred porphyrazines are those in which anaromatic group such as benzo or naptho group (substituted orunsubstituted) is present on each pyrrole nucleus. For example,phthalocyanines and napthalocyanines are respectively provided by benzoand naptho group substitution: ##STR1##

The highly conjugated planar molecular structures of phthalocyaninesubunits, their chemical flexibility and the accessibility of multipleredox states renders phthalocyanines a particularly attractiveorganoconductor component, provided suitable fabrication methods areavailable, as previously indicated.

In the provision of covalently bonded cofacially stacking porphyrazinessuch as phthalocyanines, the core ligand may be coordinated with corecomponents M such as silicon having remaining covalent bonding capacityafter coordination with the core ligand, which may be utilized forcofacially bonding phthalocyanine subunits in cofacially bonding polymerstacks having a subunit stacking repeat distance which is determined atleast in part by the covalent bond length: ##STR2##

Desirably the cofacially stacking organomacrocycle subunits which arecovalently bound in stacked array may be of substantially uniformchemical composition. However, it is also contemplated thatorganomacrocycle subunits of differing chemical composition may becopolymerized to provide desired electronic or physical characteristics.For example, unsubstituted dihydroxy silicon phthalocyanine polymerprecursors may be copolymerized with different polymer precursors suchas dihydroxy silicon (3-methyl)₄ phthalocyanine, dihydroxy siliconnaphthocyanine, or dihydroxy silicon porphyrins to provide randomcopolymers of cofacially stacking phthalocyanine subunits. Similarly,different phthalocyanine oligomers may be joined to provide linear blockcopolymers. Variations in the chemically flexible phthalocyaninesubunits provide a mechanism for varying the electron transportrelationship in a stacked, mixed-valence materials. For example, asindicated, lower alkyl groups such as methyl groups may be introduced atposition 3 of the isoindoline subunits of the phthalocyanine ligand. The3-substituted methyl groups project into the surrounding lattice to onlya limited extent and do not substantially interfere with the cofacialstacking of the subunits. However, such alkyl derivatives may require alarger dopant level to achieve a particular degree of fractional chargetransfer. Even n-butyl substitution may not interfere with stackingrelationships sufficiently to impede charge transport. It iscontemplated that other electron withdrawing or contributing groups(e.g., lower alkyl ether, amine or amino groups) may also be provided tomodify electronic properties. However, substitution of multiple electronwithdrawing substituents such as chloro, nitro and sulfono groups mayimpede fractional oxidation and prevent formation of an electricallyconductive fractionally oxidized state. However, such electronwithdrawing groups may promote fractional valence reduction in theprovision of n-type organoconductive compositions.

In the provision of cofacially stacking organomacrocycle polymers, it isdesirable that the polymer be substantially linear, in order to providefor desirable levels of solubility in the forming compositions describedherein. In this regard, it is desirable that the polymer precursorsutilized be substantially difunctional in their polymerizingfunctionality. However, a limited amount of polyfunctional componentswhich may result in a branching polymeric structure may be desirable forsome purposes such as chain extension to increase molecular weight orbranching to reduce the substantially one dimensional isotropy ofconductive properties provided by a system of linear polymer chains. Inthis regard, polyfunctional organomacrocycles such as phthalocyaninesubunits having multiple (e.g., 2) conjugated phthalocyanine rings inthe same conjugated plane, each coordinating with silicon may be used asa polyfunctional component useful in increasing molecular weight, or toprovide branched polymers while maintaining electric conductivitythrough the various branches of the structure.

As indicated, particularly preferred covalently bound cofaciallystacking polymers are phthalocyanine siloxane polymers. Such polymersmay be dissolved in strong Bronsted acids such as triflic acid, withoutsubstantial polymeric degradation. However, germanium and tin analogs ofsuch siloxane phthalocyanine polymers may be substantially degraded instrong Bronsted acid, possibly as a consequence of the large interplanarspacing and consequently increased stacking distance betweenphthalocyanine subunits. Copolymerization of such germaniumphthalocyanines with silicon phthalocyanines may result in stackingdistances intermediate the respective silicon and germanium bondlengths, which together with shielding by provision of appropriatesubstituents which do not interfere with the stacking may provideadditional useful covalently bonded cofacially stacking polymericcomponents.

When used as the sole polymeric component of a forming compositionsolution in a Bronsted acid solvent, the covalently bonded porphyrazinepolymer should be of fiber-forming molecular weight. The minimum averagechain length of a phthalocyanine siloxane polymer [Si(Pc)O]n produced inthe condensation polymerization may be estimated by Fourier transforminfrared spectrophotometric analysis of the Si-O stretching regionand/or by tritium labelling techniques. The degree of polymerizationshould best be at least about 140 phthalocyanine subunits, andpreferably should be at least about 100 phthalocyanine subunits inlength. The degree of polymerization may also be inferred from lightscattering data from sulfuric acid solutions, or measurements of theamount of water evolved during polymerization, and may be correlatedwith intrinsic viscosity measurements.

Various different covalently bonded cofacially stacking phthalocyaninepolymers may be dissolved in the forming composition, if desired. Italso may be desirable to blend covalently bonded cofacially stackingcomponents such as siloxane phthalocyanine polymers with ionicallybonding components such as nickel phthalocyanines to achieve specificproperties, particularly in providing solutions comprising an aramidpolymer component. Various ionicly bonding cofacially stackingcomponents may also be combined in provision of the forming compositionsand conductive articles of the present disclosure.

As indicated, the stacking distance is believed to be important inproviding electrical conductivity, and structural information in respectto cofacially stacking organomacrocycles may be obtained by x-raydiffraction measurements. In this regard, the interplanar spacing (c/2)of [Ni(Pc)]I₁.0 has been determined to be about 3.24 Angstroms, and thecorresponding separation of phthalocyanine siloxane subunits is about3.32 Angstroms. The interplanar spacings of electrically conductivesubunits may be manipulated to control electron transport properties inthe metallomacrocyclic systems, because the transport properties arerelatively insensitive to the identity of the metal ion.

The strong Bronsted acid solvent is an important component of formingsolutions utilized in the present disclosure for fabrication ofelectroconductive articles. By strong Bronsted acid is meant a strongproton donor. The Bronsted acid solvent should be selected to dissolveat least about 5 weight percent and preferably at least about 10 weightpercent, based on the total weight of the solution, of the macrocyclicorganoconductor component. When it is desired to utilize an alloyingpolymer, such as an aramid polymer, the solvent should further beselected to dissolve the alloying polymer in the desired weight ratio tothe macrocyclic organoconductor component of the solution.

Particularly preferred solvents for providing solutions comprisingphthalocyanine siloxane polymers, metallophthalocyanines and aramidalloying polymers are substituted sulfonic acids R--SO₃ H where R is ahalogenated lower alkane such as trifluoromethane. It is believed thatthe strong Bronsted acid solvent protonates the conjugated nitrogen ringof the planar macrocyclic phthalocyanine ligand to solublize thephthalocyanine nucleus. It may also be a factor in the solvatingcapability that the solvent partially oxidizes the phthalocyanine ring.The Bronsted acid solvent component should desirably have very limitedwater content, in order to limit the degrading effect on alloyingpolymer components, and to maintain the solvating power of the solvent.Particularly when utilizing aramid alloying polymers, the solvent shouldbest contain less than about two weight percent. While concentratedsulfuric acid alone is conventionally utilized for providing spinningdopes of aramid polymers and may have adequate solublizing power forionically bonding phthalocyanines, phthalocyanine siloxane polymers havelimited solubility in concentrated sulfuric acid, which may besubstantially less than the desired concentration for the provision ofarticle forming solutions in accordance with the present disclosure sothat the substituted perfluoro sulfonic acid solvent components such astriflic acid may necessarily be selected for solublizing such polymers.In addition, various solvent mixtures and solvent additives may beincluded to modify the solvating capacity of the strong Bronsted acidcomponent. Thus, the solvent component may comprise hydrofluoric acid,halogenated alkylsulfonic acids, halogenated aromatic sulfonic acids,fluorosulfuric acid, chlorosulfuric acid, halogenated acetic acids,halogenated lower alkyl alcohols and halogenated ketones or aldehydesdepending upon the particular solvent-polymer-organomacrocyclecombination that is employed. The solvent may also include dissolvedsalts for enhancing the solvent properties or for other processingpurposes.

For reasons of economy, and for reasons of effective fabrication, it isgenerally desirable that the solids concentration of theorganoconductive component and alloying polymer component (if any) be ashigh as possible while permitting the desired extrusion or other formingstep. Forming solutions of useful concentrations may appear solid orgelled at ambient temperature and melt to spinnable or extrudableliquids when the temperature is raised. Because the article shrinkageupon solvent removal is reduced, improved processing control andphysical integrity of the formed articles generally result fromincreased solids content of the forming solutions.

As previously indicated, it is an important feature of the presentdisclosure, that the conductive articles and the forming solutions usedto manufacture them, may desirably comprise an alloying polymer, whichis soluble in the strong Bronsted solvent from the organomacrocyclecomponent, and should not disrupt the cofacial stacking of theorganomacrocycle upon removal of the solvent. Polymers, particularlyincluding the aromatic polyamide polymers, which have a strong tendencyto crystallize, particularly in an anisotropic manner, have been foundto provide desirable qualities in the formed articles made fromcompositions comprising such polymers.

Aramid polymers have a strong crystallization tendency which may bemanifested as optically anisotropic solutions over quite wide ranges ofconcentration and polymer molecular weight. The tendency of rigidaromatic polyamides to lyoptropic liquid crystal formation involvesparallel orientation of large groups of rodlike molecules. Variousaromatic polyamide polymers tend to be bound strongly by hydrogenbonding forces, and form a high modulus anisotropic structure uponsolvent removal.

Aramid solutions having anisotropic phase regions exhibit acharacteristic opalescence when stirred which fades in a few secondswhen the shearing action stops, and may exhibit decreasing viscositywith increasing aramid polymer concentration as an apparent consequenceof the polymer chain association in solution.

The aramid polymer component should be of film or fiber formingmolecular weight. Aramid polymers having viscosities of at least about0.7 in sulfuric acid or other suitable solvent are reported to be fiberforming.

Various aramid polymers may be readily oriented by passage through aspinneret or other application of substantial shear, which orientationmay desirably be preserved upon coagulation of the polymer upon solventremoval. The tendency for various aramid polymers to align in ananisotropic manner, to form a structure through intermolecular polarattractions (particularly hydrogen bonding between carbonyl and aminomoieties of the amid groups) may form a structural template to faciliateor enhance the cofacial stacking or agglomeration of theorganomacrocyclic moiety.

Aromatic polyamides are well known and substantial work has been carriedout in the polymerization, manufacture and processing of such polymers,such as described in U.S. Pat. Nos. 3,767,756 and Re. 30,352, which areincorporated herein by reference. Among the suitable alloying aromaticpolyamides are those in which the chain extending bonds from eacharomatic nucleus are essentially coaxial or parallel and oppositelydirected. The term "aromatic nucleus" includes individual andpolynuclear aromatic rings and divalent radicals.

Aromatic linear polyamides are characterized by recurring units of theformula --[R--A]-- where R comprises a divalent aromatic radical and Ais an amide group, which may be of either ##STR3## orientation.

The aromatic nuclei of the polyamide polymers may bear substituents,which should desirably not cause cross-linking or insolubility of thealloying aramid polymer during processing, but which may, if desired,provide for crosslinking of the formed article. Both homo- andco-polyamides having substituted or unsubstituted aromatic nuclei may beutilized as alloying polymers, and as indicated, the amide constituentmay have varying orientation, and randomly copolymerized amide-formingconstituents may be of AB (e.g., from p-aminobenzoyl chloridehydrochloride), AA (e.g., from p-phenylene-diamine or2,6-dichloro-p-phenylene diamine) or BB (e.g., from terephthaloyl or4,4'-bibenzoyl chloride) type or mixtures thereof.

Various aromatic polyamides which may be useful as alloying componentsin conductive articles and forming compositions includepoly(p-benzamide); poly(p-phenylene terephthalamide);poly(2-chloro-p-phenylene 2,6-naphtha- 1amide); poly(p-phenylenep,p'-biphenyldicarboxamide); poly(p,p'-phenylene benzamide); poly(1,5-napththylene terephthalamide); ordered aromatic copolyamides suchas e.g., copoly(p,p'-diaminobenzanilideterephthalamide) and randomcopolyamides such as e.g., copoly(p-benzamide/m-benzamide) (95/5);poly(p-phenylene 1,5-naphthalenedicarboxamide); poly(trans,trans-4,4'-dodecabydropbiphenylene terephthalamide);poly(trans-1,4-cinnamamide); poly(p-phenylene4,8-quinolinedicarboxamide); poly(1,4-[2,2,2]-bicyclo-octyleneterephthalamaide); copoly(p-phenylene4,4'-azoxybenzenedicarboxamide/terephthalamide); poly(p-phenylene4,4'-trans-stilbenedicarboxamide) and poly(p-phenyleneacetylenedicarboxamide).

In the preparation of forming compositions comprising an amide alloyingpolymer, dissolution of the polyamide and the organomacrocycle componentmay be carried out by mixing these components with the selected Bronstedacid solvent, desirably under conditions of mild shear and at elevatedtemperature, preferably in the range of from about 70° to about 100° C.The forming compositions and the conductive articles formed therefrommay include solid particulate additives such as magnetic orelectroconductive fibers or powders. For example, magnetic oxides havinga high magnetic susceptibility, graphite particles, or other conductivefibers or reinforcements which are substantially insoluble in thesolution may be incorporated in the forming solutions and will beincorporated in the formed articles upon removal of the Bronstedsolvent. For purposes of the present disclosure, such additives are notconsidered to be utilized in the weight percent calculations of thesolution because they are not dissolved in the composition solvent, andare to be excluded from the weight percentage determination in respectto the conductive matrix of the formed electroconductive articlesthemselves.

As indicated, the organomacrocycle component is provided in a fractionalvalence state in the manufacture of electroconductive circuit devices,fibers, coatings, films and other articles in accordance with thepresent disclosure. Provision of the fractional valence state may becarried out by including a suitable redox doping agent in the formingsolution, by pre-treatment prior to dissolution in the provision of theforming composition or by post-treatment of the formed article afterremoval of the solvent component. By "fractional valence" is meant nonintegral formal oxidation states generally having a value between zeroand one. Porphyrazines such as phthalocyanines generally tend to havefractional valence oxidation states of about one-third in respect toeach subunit of the cofacial array.

The organomacrocyclic component may be subjected to redox treatment in avariety of different ways to provide a desired fractional valence state,depending in part on the cofacially stacking component. In this regard,the covalently bound compositions may be subjected to a broader range oftreatment than monomeric or molecular cofacially stacking compositionswhich rely on crystallization forces to achieve a cofacially stackedcondition. Contacting the formed article with solutions of iodine inorganic solvents or exposing the article to iodine vapor results insubstantial iodine uptake. Alternatively, covalently bonded cofaciallystacking polymers such as [Si(Pc)O]n may be doped by dissolving in astrong Bronsted acid such as triflic acid and removing the solvent bycontact with an aqueous I₃ ⁻ solution. The stoichiometries which areobtained depend upon the reaction conditions. The oxidation is believedto be ligand centered, producing arrays of cation radicals. Desirably,substantially all of the cofacially stacking components will be in afractional valence state.

Halogens are known to be especially effective acceptors for stabilizinglow-dimensional fractional valence arrays and are particularly effectiveat partially oxidizing metallomacrocycles. For a wide spectrum ofdonors, including phthalocyanines and porphyrins, the gas phaseionization potentials of the fractional valence oxidant fall within anarrow range between about 6.25 and 7. Halogens are not the onlyacceptors that form mixed valence material with organic donors. Organicoxidants such as the high potential quinones shown below form a widerange of partially oxidized conductive salts: ##STR4##

Conductive, mixed valent metallomacrocyclic arrays may be produced byquinone oxidants when segregated stacking is guaranteed by cofacialcovalent bonding, but may not produce conductive, cofacially stackedsystems when utilizing monomeric or molecular compositions which rely oncrystallization forces. Large increases in electrical conductivityaccompany quinone doping of the face-to-face phthalocyanine polymers.Suitable doping agents may further include polymeric compositions suchas polymeric sulfonic acids (e.g., perflourosulfonic substitutedpolytetrafluoroethylenes such as Nafion), provided such materials aresoluble in the solvent or a post-forming redox treatment solution.Polymeric doping agents may also be utilized through solution treatmentto provide a surface treatment of the formed article. Polymeric dopingagents may have limited utility with ionicly bonding organomacrocyclesbecause of potential interference with cofacially stacking of suchcomponents, and accordingly may find principal utility with covalentlybonded cofacially stacking organomacrocycles, where it is desired tohave limited surface treatment effects, or where it is desired toprevent migration of fractional valence counterions, as in the provisionof device junctions or composite interfaces. As indicated, the redoxdopant may be provided in a coagulation both for the forming sulution,ore may be provided in a treatment solution applied to the formedarticles after the Bronsted solvent has been removed. In this latterregard, treatment with nitrosyl salts is an effective means forintroducing a variety of counterirons in the provision of the fractionalvalence state in both covalently bonded and ionicly stackingphthalocyanine compositions. For example, formed articles may becontacted with solutions of NO⁺ X⁻ salts (e.g. in methyl chloride) whereX⁻ is a suitable inorganic counteriron such as BF₄ ⁻, PF₆ ⁻, etc. Uponoxidation of the organomacrocycle component, nitrous oxide is releasedand the anion of the nitrosyl salt is incorporated in the fractionalvalence composition thus formed. Similarly, the organomacrocycle may beoxidyzed or reduced by contact with solutions of higher valent inorganicsalts such as FeCl₃, IrCl₆ 2 salts, Pb(OAc)₄, organic peroxides, oralkali metal organometallic compounds. The materials may also besubjected to redox treatment in the vapor phase, as by contacting theorganocyclic component with iodine or potassium vapor for oxidation orreduction respectively. The fractional valence state may also beprovided by electrochemical redox treatment of the formed article afteror contemporaneously with solvent removal by temporarily incorporatingthe formed polymer object as the anode or cathode in an electrochemicalcell containing a suitable organic electrolyte (e.g., acetonitrile,propylene carbonate, tetrahydrofuran) and soluble alkali or organic salt(e.g., M⁺ X⁻ or , R⁺ X⁻, where M is an alkali metal such as sodium orlithium, etc., where X⁻ is an anion such as CiO₄ ⁻, BF₄ ⁻, PF₆ ⁻, etc.and where R⁺ is an organocation such as N(C₄ H₉)₄ ⁺, P(C₄ H₉)⁺ ₄, etc. Apotential in the range of from about 0.1 to about 3 volts may beimpressed upon the cell and current may be impressed upon the cell andcurrent is passed until the polymer reaches the desired degree ofoxidation or reduction. Such electrochemical redox treatment isparticularly useful in respect to covalently bonded cofacially stackingpolymers. When stacked donor microstructure is necessarily provided bycovalent bonding, mixed valent conductive assemblies may be producedwith a broad range of oxidants or counterions.

Reduction of metallophthalocyanines using alkali metals may fail toprovide coductive cofacially stacked arrays of ionicly bondingcomponents apparently because of stocking disruption, but covalentlybound cofacially stacked moieties may be more readily provided inreduced mixed valence state.

As indicated, in accordance with method aspects of the presentdisclosure, the forming composition, which is a viscous or plasticfluid, is formed into a desired shape prior to solidification. Aparticularly desirable method of forming conductive articles is byextrusion of the forming composition through a suitable extrusionorifice into a coagulating fluid which is capable of removing thesolvent without dissolving the solid constituents of the formingsolution.

The extrusion orifice may be separated from the coagulating fluid by anintermediate layer directly into a coagulating fluid. In this regard, anintermediate fluid layer of gas or a non-coagulating liquid such astoluene or heptane may be provided to effect equilibration of theextruded form, to carry out fractional redox treatment, to effecttemperature reduction, or to control the rate of solidification.

A variety of coagulating baths may be used to coagulate the formedarticle, and in this regard, both aqueous and non-aqueous systems may beutilized. Aqueous systems may contain high concentrations of the solventof the forming compositions (e.g., triflic acid), or basic materialssuch as ammonium hydroxide or other salts in accordance withconventional practice in the manufacture of aramid fibers. Aqueous bathsmay further include water miscible organic solvents such as methanol andethylene glycol to moderate or control the solidification of the formedarticles and the removal of the Bronsted acid solvent. Non-aqueouscoagulating baths such as baths comprising methanol or other loweralcohols may also be utilized. The coagulating bath temperature maydesirably be less than that at which the forming composition isextruded. In this regard, the forming composition may desirably beextruded or otherwise formed at elevated temperatures such as in therange of from about 70° to about 100° C. to reduce the solutionviscosity. The extruded fiber or other formed article may desirably becooled upon removal of the solvent acid and in this regard the formingimposition may be formed into the desired shape at an elevatedtemperature, and may desirably be contacted with a coagulation bath at alower temperature in the range from about 20° to about 40° C., althoughambient temperature processing is desirable for practicalconsiderations.

It is desirable to remove substantially all of the Bronsted acidcomponent by thoroughly washing the fiber or other solidified form,except that desired to provide a fractional valence salt with thecofacially stacking organomacrocycle component. This is particularlytrue of compositions comprising an aramid or other polymer which maydegrade in the presence of acid.

The thoroughly washed fibers may be treated at elevated temperature(e.g., up to 150° C.) either under a slight tension or without tension,depending upon the physical properties desired in the fiber, to removemoisture or other volatile coagulation bath components. The propertiesof the fibers comprising an aramid alloying constituent may also bealtered by heat treatment, desirably under tension in an inertatmosphere at temperatures in the range of 150° C. to 550° C. or more.

As previously described in respect to FIG. 1, homogeneous fibers may beprovided by means of relatively simple fiber spinning apparatus.Composite fibers may also be provided by means of compound extrusionapparatus. Illustrated in FIG. 10, is a cross sectional view of compoundextrusion apparatus suitable for fabrication of compositeelectroconductive articles. The apparatus 1000 comprises twoindependently controllable extrusion assemblies 1002, 1004, which in theillustrated embodiment 1000 are substantially identical. The assemblies1002, 1004 each comprise a central polytetrafluorethylene body 1006having a central bore 1008 which serves as a reservoir for the materialto be extruded. A close fitting plunger 1010, which may be forced intothe bore 1008 in a controlled predetermined manner by motorizedapparatus (not shown), serves to force the extrusion composition fromthe reservoir through a conduit 1012 having a stopcock valve 1014 tocontrol passage therethrough. Each of the extrusion mechanisms 1002,1004 is provided with a nitrogen flush conduit 1016 to maintain thecomposition in an inert atmosphere. The material forced from thereservoir of the device 1002 is conducted by conduit 1018 to an internalzone of a compound orifice 1020 surrounding the internal conduit ofcompound orifice 1020. The material forced from the reservoir of thedevice 1004 is transported by conduit 1022 to a centrally locatedinternal conduit of the conduit 1024 of the compound orifice 1020, thelower end 1026 of which is shown partially broken away to reveal thetermination therein of the central conduit 1024. The body of the devices1102, 1104, the conduits 1018, 1022 and the compound orifice assembly1020 may be heated if desired, as by electrical heating tape.

As illustrated in FIG. 10, one organomacrocyclic forming composition1032 in accordance with the present disclosure may be extruded through acentral orifice 1034, while a different composition 1036, which may, forexample, be a different forming composition or an aramid dope which doesnot include a cofacially stacking component, may be simultaneouslyextruded through the surrounding orifice 1038 at a substantially similarextrusion rate as the composition 1036. The resulting formed compositestructure may be solidified and subjected to redox treatment to form afractional valence conductive fiber having a composite structure. It isdesirable that the parameters of the forming compositions such as solidscontent and viscosity be matched in composite structures to avoidbuckling or differential shrinkage in the formation of such structures.Films may be provided by extrusion in a similar manner by using anelongated orifice.

As previously indicated, the organomacrocyclic solutions may be formedby procedures other than extrusion. In this regard, illustrated in FIG.11 is a printed circuit device 1100 comprising a substantially inertsubstrate 1102, which substrate is substantially unaffected by strongBronsted solvents, a printed circuit capacitor element 1104 and aprinted circuit inductor element 1106. The printed circuit 1100 isfabricated by printing a first structural layer 1108 of a suitableforming composition comprising a cofacially stacking porphyrazinecompound directly on to the substrate 1102. The first layer comprisesthe lower electrode 1110 of capacitor 1104, terminal connector element1112 and spiral inductor element 1114. The circuit configuration may beprinted on the substrate in any appropriate conventional manner,provided materials are used which are not substantially adverselyaffected by the composition of the solution. The Bronsted solvent issubsequently removed from the first level 1108 to solidify the formedelements 1112, 1110, 1114 on the substrate, which are also subjective toappropriate redox treatment. An intermediate insulating layer 1116 isthen provided, as by coating from solution, over the layer 1108. Theintermediate layer may be any compatible dielectric layer, incuding aninsulating aramid polymer layer. Subsequently, a third level 1118comprising an upper capacitor electrode 1120 and an inductor terminal1122 is printed over the intermediate insulating layer 1116, with theterminal 1122 making contact with the inductor 1106 at its centraltermination. The solvent is then removed from the upper layer 1118 tosolidify the electrical components, and the layer is subjected toappropriate redox treatment to provide a printed LC circuit. Device 1100is only illustrative of printed circuit devices generally, and manyother circuit applications may be provided.

Various aspects of fiber manufacture will now be further described byreference to the following specific examples.

EXAMPLE 1

100 mg. of aramid pulp sold under the trade name Kevlar 29 by E. I.DuPont and DeNemours & Co., Inc. (hereinafter referred to as DuPont) and100 mg. of silicon phthalocyanine polymer [Si(Pc)O]n is dissolved in 1milliliter of triflic acid to provide a dark green spinning solutionhaving about 10 weight percent solids. The solution is introduced into asyringe like that of FIG. 1, having a #23 stainless steel needle cut toa length of 1 cm, and having an internal diameter of 0.33 mm. Thespinning solution is extruded through the needle by applying continuouspressure to the syringe plunger to extrude the solution directly into awater coagulation bath. Upon drying, strong, purplish black, smoothsurfaced fibers are provided.

EXAMPLE 2

100 mg. of Kevlar 29 aramid polymer of Dupont as described in Example 1and 200 mg. of silicon phthalocyanine polymer [Si(Pc)O]n is dissolved in1 milliliter of triflic acid to provide a dark green spinning solutionto provide a solids weight percent about 14%. The solution is introducedinto a syringe having a #23 stainless steel needle cut to a length of 1cm, and having an internal diameter of 0.3 mm. The spinning solution isextruded through the needle by applying continuous pressure to thesyringe plunger to extrude the solution directly into a watercoagulation bath. Upon drying, strong, purplish black, smooth surfacefibers are provided. The syringe is maintained at a temperature of about90°-110° C. by means of a heating tape. Black fibers having aconductivity of about 3×10⁻³ ohms⁻¹ cm⁻¹ are provided which are smooth,but weaker and less flexible than the fibers of Example 1.

EXAMPLE 3

100 mg. of Kevlar 29 aramid polymer of Dupont as described in Example 1and 300 mg. of silicon phthalocyanine polymer [Si(Pc)O]n is dissolved in1 milliliter of triflic acid to provide a dark green spinning solutionsolids content of about 18 weight percent. The solution is introducedinto a syringe having a #23 stainless steel needle cut to a length of 1cm, and having an internal diameter of 0.3 mm. The spinning solution isextruded through the needle by applying continuous pressure to thesyringe plunger to extrude the solutibn directly into a watercoagulation bath. After drying, strong, purplish black, smooth surfacefibers are provided which are subsequently doped by treatment withbromine solution. The fiber conductivity is measured by conventionalfour probe D C conductivity testing at different temperatures, as shownin FIG. 3. The syringe is maintained at a temperature of about 90°-110°C. by means of a heating tape.

EXAMPLE 4

0.57 grams of silicon phthalocyanine [Si(Pc)O]n is dissolved in 1milliliter of CF₃ SO₃ H. The components are mixed at 100° C. and beforespinning, the solution is again heated to 100° C. The spinning solutionis extruded through a #23 stainless steel needle having a length of 1 cmthrough an air gap of 3 to 5 cm into an aqueous coagulation bathcontaining Iodine and acetone. The fiber is electroconductive and has ashiny surface even in the dried state.

EXAMPLE 5

200 mg. of sublimed nickel phthalocyanine [Ni(Pc)] and 100 mg. of Kevlar29 aramid of Dupont are dissolved in 1 cc of CF₃ SO₃ H at a temperatureof about 100° C. The spinning solution is transferred to a syringe witha #23 needle which is maintained at 90° C. by means of an electricalheating tape. The spinning solution is forced through a water bathcontaining 0.2 weight percent of potassium iodide and 0.2 weight percentof iodine dissolved therein. The extruded fibers have a shiny surface,even after drying. The fiber conductivity is measured by conventionalfour probe conductivity testing at different temperatures, as shown inFIG. 6.

EXAMPLE 6

300 mg. of sublimed nickel phthalocyanine [Ni(Pc)] and 100 mg. of Kevlar29 aramid of Dupont are dissolved in 1 cc of CF₃ SO₃ H at a temperatureof about 100° C. for one hour and allowed to stand at room temperatureovernight. The spinning solution is transferred to a syringe with a #23needle which is maintained at 90° C. by means of an electrical heatingtape. The spinning solution is forced through a water bath containing0.2 weight percent of potassium iodide and 0.2 weight percent of iodinedissolved therein. The extruded fibers are electroconductive and have ashiny surface, even after drying.

EXAMPLE 7

300 mg. of [Si(Pc)O]n is dissolved in 1 ml of CF₃ SO₃ H and is mixed at90° C. in the spinning apparatus. The solution is spun through a #23needle cut to a length of 1 mm. into an aqueous coagulation bath. Thedried fiber has a room temperature conductivity of about 4.5×10⁻² ohms⁻¹cm⁻¹ without additional doping.

EXAMPLE 8

300 mg. of nickel phthalocynanine and 100 mg. of Kevlar 29 aramid pulpof Dupont are dissolved in 1 ml. of triflic acid and the solution isspun into fibers in a manner similar to Example 6 and the fibers aresubsequently iodine doped after spinning. Conventional four probe D Cconductivity testing is carried out on the fibers, as shown in FIG. 2.

EXAMPLE 9

400 mg. of silicon phthalocynanine polymer is dissolved in 1 ml. oftriflic acid to provide a 24 weight percent solution which is spun intofibers in a manner similar to Example 4. Fibers from different runs aresubsequently doped with iodine and bromine, respectively. CXonventionalfour probe D C conductivity measurements are made of the iodine andbromine doped fibers, as shown in FIGS. 4 (iodine doped) and 5 (brominedoped), respectively.

EXAMPLE 10

Two runs are made in a manner similart to Example 6 using formingsolutions consisting of 300 mg. of nickel phthalocyanine and 100 mg. ofKevlar 29 aramid pulp from Dupont dissolved in 1 ml. of triflic acid.One run is spun into an ^(I) 3 containing aqueous coagulation bath.Another run is s pun into an aqueous bath and subsequently Bromine dopedby contact with a bromine-contaning benzene solution. Conventional fourprobe D C conductivity measurements are made of the fibers, as shown inFIG. 7 (Iodine-doped) and FIG. 8 (Bromine-doped).

EXAMPLE 11

300 mg. of nickel phthalocyanine iodide Ni (Pc) I₁.0 and 100 mg. ofKevlar 29 aramid from Dupont are dissolved in 1 ml. of triflic acid andspun into a water bath in a manner similar to the previous examples. Nosubsequent doping was carried out. Conventional four probe D Cconductivity measurements of the resulting fiber are carried out, asshown in FIG. 9.

It will be appreciated that in accordance with the present disclosure,improved methods and forming compositions for readily fabricatingelectroconductive articles have been provided, as well as newelectroconductive articles themselves.

While various aspects of the present disclosure have been described withspecific reference to particular embodiments, it will be appreciatedthat various modifications, adaptations and alterations may be madewithin the spirit and scope of the present disclosure and are intendedto be within the scope of the following claims.

What is claimed is:
 1. A forming composition for fabricating low dimensionally electroconductive articles comprising a viscous solution having at least about 3 percent by weight, based on the total weight of said solution, of a cofacially stacking ionically bonding porphyrazine, of the general formula (Pc)M_(n) where Pc comprises pyrrole nuclei linked by nitrogen atoms to form a conjugated planar ligand having in a neutral state a 22 pi electron conjugation system, m comprises an ion selected from the group consisting of hydrogen ion and polyvalent transition metal ions and n is an integer, at least about three weight percent of a polyamide, and a strong Bronsted acid solvent, the weight ratio of said porphyrazine to said polyamide being at least about 1:3.
 2. A conductive article forming composition in accordance with claim 1 wherein said polyamide is an aramid polymer of fiber forming molecular weight.
 3. A conductive article forming composition in accordance with claim 1 wherein said ionically bonding porphyrazine is a divalent metallo phthalocyanine having a stacking distance of less than about 3.4 Angstroms, and wherein said Bronsted acid solvent comprises trifluoro methane sulfonic acid.
 4. A conductive article forming composition in accordance with claim 1 wherein said phthalocyanine is nickel phthalocyanine.
 5. A forming composition for fabricating low dimensional electroconductive articles of predetermined form comprising a solution having an ionically bonding cofacially stacking fractional valence porphyrazine, said porphyrazine selected from the group of: ##STR5## where M=a divalent transition metal; R=H, CH₃, or an alkyl group; and an aromatic polyamide for providing structural integrity to said article, said polyamide having aromatic nuclei devoid of substituents capable of disrupting the cofacial stacking of said porphyrazine component.
 6. The forming composition of claim 5 wherein said ratio of aromatic polyamide to said porphyrazine polymer ranges from 3:1 to 1:1.
 7. The forming composition of claim 5 wherein said polyamide is of film forming molecular weight.
 8. The forming composition of claim 5 wherein said polyamide is of fiber forming molecular weight.
 9. The forming composition of claim 5 wherein said polymide is selected from the group of:poly(p-benzamide); poly(p-phenylene terephthalamide); poly(2-chloro-p-phenylene 2, 6-naphtha-1-amide); poly(p-phenylene p,p'-biphenyldicarboxamide); poly(p,p'-phenylene benzamide); poly(1,5-naphthylene terephthalamide); copoly(p,p'-diaminobenzaniliditerephthalamide), copoly(p-benzamide/m-benzamide); poly(p-phenylene 1,5-naphthalenedicarboxamide); poly(trans, trans-4,4'-dodecahydrobiphenylene terephthalamide); poly(trans-1,4-cinnamamide); poly(p-phenylene 4,8-quinolinedicaboxamide); poly(1,4- [2,2,2]-bicyclo-octylene terephthalamide); copoly(p-phenylene 4,4'-azoxybenzene-dicarboxamide/terephthalamide); poly(p-phenylene 4,4'-trans-stilbenedicarboxamide) and poly(p-phenylene acetylenedicarboxamide). 